CHEMISTRY STOICHIOMETRY

Transcription

1 CHEMISTRY STOICHIOMETRY Equivalent mass of elements - definition, principles involved in the determination of equivalent masses of elements by hydrogen displacement method, oxide method, chloride method and inter conversion method (experimental determination not needed). Numerical problems. Equivalent masses of acids, bases and salts. Atomic mass, Molecular mass, vapour density-definitions. Relationship between molecular mass and vapour density. Concept of STP conditions. Gram molar volume. Experimental determination of molecular mass of a volatile substance by Victor Meyer s method. Numerical problems. Mole concept and Avogadro number, numerical problems involving calculation of: Number of moles when the mass of substance is given, the mass of a substance when number of moles are given and number of particles from the mass of the substance. Numerical problems involving mass-mass, massvolume relationship in chemical reactions. Expression of concentration of solutions-ppm, normality, molarity and mole fraction. Principles of volumetric analysis- standard solution, titrations and indicators-acid-base (phenolphthalein and methyl orange) and redox (Diphenylamine). Numerical problems. ATOMIC STRUCTURE Introduction- constituents of atoms, their charge and mass. Atomic number and atomic mass. Wave nature of light, Electromagnetic spectrum-emission spectrum of hydrogen-lyman series, Balmer series, Paschen series, Brackett series and Pfund series. Rydberg s equation. Numerical problems involving calculation of wavelength and wave numbers of lines in the hydrogen spectrum. Atomic model- Bohr s theory, (derivation of equation for energy and radius not required). Explanation of origin of lines in hydrogen spectrum. Limitations of Bohr s theory. Dual nature of electron- distinction between a particle and a wave. de Broglie s Theory. Matter-wave equation (to be derived). Heisenberg s uncertainty principle (Qualitative). Quantum numbers - n, l, m and s and their significance and inter relationship. Concept of orbital- shapes of s, p and d orbitals. Pauli s Exclusion Principle and Aufbau principle. Energy level diagram and (n+1) rule. Electronic configuration of elements with atomic numbers from 1 to 54. Hund s rule of maximum multiplicity. General electronic configurations of s, p and d block elements. PERIODIC PROPERTIES Periodic table with 18 groups to be used. Atomic radii (Van der Waal and covalent) and ionic radii: Comparison of size of cation and anion with the parent atom, size of isoelectronic ions. Ionization energy, electron affinity, electronegativity- Definition with illustrations. Variation patterns in atomic radius, ionization energy, electron affinity, electronegativity down the group and along the period and their interpretation. OXIDATION NUMBER Oxidation and reduction-electronic interpretation. Oxidation number: definition, rules for computing oxidation number. Calculation of the oxidation number of an atom in a compound/ion. Balancing redox equations using oxidation number method, calculation of equivalent masses of oxidising and reducing agents. GASEOUS STATE GAS LAWS: Boyle s Law, Charles Law, Avogadro s Hypothesis, Dalton s Law of partial pressures, Graham s Law of diffusion and Gay Lussac s Law of combining volumes. Combined gas equation. Kinetic molecular theory of gases-postulates, root mean square velocity, derivation of an equation for 7 P age

2 the pressure exerted by a gas. Expressions for r.m.s velocity and kinetic energy from the kinetic gas equation. Numerical problems. Ideal and real gases, Ideal gas equation, value of R (SI units). Deviation of real gases from the ideal behaviour. PV-P curves. Causes for the deviation of real gases from ideal behavior. Derivation of Van der Waal s equation and interpretation of PV-P curves CHEMICAL KINETICS Introduction. Commercial importance of rate studies. Order of a reaction. Factors deciding the order of a reaction-relative concentrations of the reactants and mechanism of the reaction. Derivation of equation for the rate constant of a first order reaction. Unit for the rate constant of a first order reaction. Half-life period. Relation between half-life period and order of a reaction. Numerical problems. Determination of the order of a reaction by the graphical and the Ostwald s isolation method. Zero order, fractional order and pseudo first order reactions with illustrations. Effect of temperature on the rate of a reaction-temperature coefficient of a reaction. Arrhenius interpretation of the energy of activation and temperature dependence of the rate of reaction. Arrhenius Equation. Influence of catalyst on energy profile. Numerical problems on energy of activation. ORGANIC COMPOUNDS WITH OXYGEN-2, AMINES Phenols Uses of phenol. Classification: Mono, di and tri-hydric Phenols Isolation from coal tar and manufacture by Cumene Process. Methods of preparation of phenol from - Sodium benzene sulphonate, Diazonium salts Chemical properties: Acidity of Phenols-explanation using resonance-effect of substituents on Acidity (methyl group and nitro group as substituents), Ring substitution reactions-bromination, Nitration, Friedel-craft s methylation, Kolbe s reaction, Reimer-Tiemann reaction. Aldehydes and Ketones: Uses of methanal,benzaldehyde and acetophenone Nomenclature General methods of preparation of aliphatic and aromatic aldehydes and ketones from Alcohols and Calcium salts of carboxylic acids Common Properties of aldehydes and ketones a) Addition reactions with - Hydrogen cyanide, sodium bisulphate b) Condensation reactions with-hydroxylamine, Hydrazine, Phenyl hydrazine, Semicarbazide c) Oxidation. Special reactions of aldehydes: Cannizzaro s reaction-mechanism to be discussed, Aldol condensation, Perkin s reaction, Reducing properties-with Tollen s and Fehling s reagents. Special reaction of ketones-clemmensen s reduction Monocarboxylic Acids Uses of methanoic acid and ethanoic acid. Nomenclature and general methods of preparation of aliphatic acids From Alcohols, Cyanoalkanes and Grignard reagent General properties of aliphatic acids: Reactions with - Sodium bicarbonate, alcohols, Ammonia, Phosphorus pentachloride and soda lime Strength of acids-explanation using resonance. Effect of substituents (alkyl group and halogen as substituents) Amines 8 P age

3 Uses of Aniline Nomenclature Classification-Primary, Secondary, Tertiary-aliphatic and aromatic. General methods of preparation of primary amines from - Nitro hydrocarbons, Nitriles (cyano hydrocarbons), Amides(Hoffmann s degradation) General Properties - Alkylation,Nitrous acid, Carbyl amine reaction, Acylation Tests to distinguish between-primary, secondary, Tertiary amines-methylation method. Interpretation of Relative Basicity of-methylamine, Ammonia and Aniline using inductive effect. HYDROCARBONS-2 Stability of Cycloalkanes-Baeyer s Strain theory-interpretation of the properties of Cycloalkanes, strain less ring. Elucidation of the structure of Benzene - Valence Bond Theory and Molecular Orbital Theory. Mechanism of electrophilic substitution reactions of Benzene-halogenations, nitration, sulphonation and Friedel Craft s reaction. HALOALKANES Monohalogen derivaties: Nomenclature and General methods of preparation from-alcohols and alkenes. General properties of monohalogen derivatives: Reduction, with alcoholic KOH, Nucleophilic substitution reactions with alcoholic KCN, AgCN and aqueous KOH, with Magnesium, Wurtz Reaction, Wurtz-Fittig s Reaction, Friedal-Craft s Reaction Mechanism of Nucleophilic Substitution reactions- SN1 mechanism of Hydrolysis of tertiary butyl bromide and SN2 mechanism of Hydrolysis of methyl bromide. COORDINATION COMPOUNDS Co-ordination compound: Definition, complex ion, ligands, types of ligands-mono, bi, tri and polydentate ligands. Co-ordination number, isomerism (ionization linkage, hydrate), Werner s Theory, Sidgwick s Theory, and E A N rule, Nomenclature of coordination, compounds. Valence Bond Theory: sp 3, dsp 2 and d 2 sp 3 hybridisation taking [Ni(Co)4], [Cu(NH 3 ) 4 ]SO 4, K 4 [Fe(CN)6] respectively as examples. CHEMICAL BONDING 2 Covalent bonding-molecular orbital theory :linear combination of atomic orbitals (Qualitative approach), energy level diagram, rules for filling molecular orbitals, bonding and anti bonding orbitals, bond order, electronic configuration of H2, Li2 and O2 Non existence of He2 and paramagnetism of O2. Metallic bond: Electron gas theory (Electron Sea model), definition of metallic bond, correlation of metallic properties with nature of metallic bond using electron gas theory. CHEMICAL THERMODYNAMICS-2 Spontaneous and non-spontaneous process. Criteria for spontaneity-tendency to attain a state of minimum energy and maximum randomness. Entropy - Entropy as a measure of randomness, change in entropy, unit of entropy. Entropy and spontaneity. Second law of thermodynamics. Gibbs free as a driving force of a reaction Gibbs Equation. Prediction of feasibility of a process in terms of G using Gibbs Equation. Standard free energy change and its relation to Kp (equation to be assumed). Numerical problems. SOLID STATE Crystalline and amorphous solids, differences. Types of crystalline solids - covalent, ionic, molecular and metallic solids with suitable examples. Space lattice, lattice points, unit cell and Co- ordination number. Types of cubic lattice-simple cubic, body centered cubic, face centered cubic and their coordination 9 P age

4 numbers. Calculation of number of particles in cubic unit cells. Ionic crystals-ionic radius, radius ratio and its relation to co-ordination number and shape. Structures of NaCl and CsCl crystals. ELECTROCHEMISTRY Electrolytes and non-electrolytes. Electrolysis-Faraday s Laws of electrolysis. Numerical problems. Arrhenius theory of electrolytic dissociation, Merits and limitations. Specific conductivities and molar conductivity-definitions and units. Strong and weak electrolytes-examples. Factors affecting conductivity. Acids and Bases: Arrhenius concept, limitations. Bronsted and Lowry s concept, merits and limitations. Lewis concept, Strengths of Acids and Bases - dissociation constants of weak acids and weak bases. Ostwald s dilution law for a weak electrolytes-(equation to be derived) - expression for hydrogen ion concentration of weak acid and hydroxyl ion concentration of weak base - numerical problems. Ionic product of water. ph concept and ph scale. pka and pkb values-numerical problems. Buffers, Buffer action, mechanism of buffer action in case of acetate buffer and ammonia buffer. Henderson s equation for ph of a buffer (to be derived). Principle involved in the preparation of buffer of required ph-numerical problems. Ionic equilibrium: common ion effect, solubility. 2B and AB2product, expression for Ksp of sparingly soluble salts of types AB, A B2Relationship between solubility and solubility product of salts of types AB, A. Applications of common ion effect and solubility product in inorganic2and AB qualitative analysis. Numerical problems. Electrode potential: Definition, factors affecting single electrode potential. Standard electrode potential. Nernst s equation for calculating single electrode potential (to be assumed). Construction of electro-chemical cells-illustration using Daniel cell. Cell free energy change [ Go =-nfeo (to be assumed)]. Reference electrode: Standard Hydrogen Electrode-construction, use of SHE for determination of SRP of other single electrodes. Limitations of SHE. Electrochemical series and its applications. Corrosion as an electrochemical phenomenon, methods of prevention of corrosion. ORGANIC CHEMISTRY Inductive effect, Mesomeric effect and Electromeric effect with illustrations, Conversion of methane to ethane and vice versa and Methanol to ethanol and vice versa ISOMERISM-2 Stereo isomerism: geometrical and optical isomerism Geometrical isomerism-illustration using 2-butene, maleic acid and fumaric acid as example, Optical Isomerism-Chirality, optical activity-dextro and Laevo rotation (D and L notations). CARBOHYDRATES Biological importance of carbohydrates, classification into mono, oligo and poly saccharides. Elucidation of the open chain structure of Glucose. Haworth s structures of Glucose, Fructose, Maltose and Sucrose (elucidation not required). OILS AND FATS Biological importance of oils and fats, Fatty acids-saturated, unsaturated, formation of triglycerides. Generic formula of triglycerides. Chemical nature of oils and fats-saponification, acid hydrolysis, rancidity refining of oils, hydrogenation of oils, drying oils, iodine value. AMINO ACIDS AND PROTEINS Aminoacidsa Biological importance of proteins, - General formula Formulae and unique feature of glycine, alanine, serine, cysteine, aspartic acid, lysine, tyrosine and proline. Zwitter ion, amphiprotic nature, isoelectric point, peptide bond, polypeptides and proteins. 10 P age

5 Denaturation of proteins Structural features of Insulin - a natural polypeptide. METALLURGY 2 Physico-chemical concepts involved in the following metallurgical operations - Desilverisation of lead by Parke s process-distribution law. Reduction of metal oxides - Ellingham diagrams - Relative tendency to undergo oxidation in case of elements Fe Ag, Hg, Al, C. Cr, and Mg. Blast furnace - metallurgy of iron - Reactions involved and their role, Maintenance of the temperature gradient, Role of each ingredient and Energetics INDUSTRIALLY IMPORTANT COMPOUNDS Manufacture of Caustic soda by Nelson s cell Method, Ammonia by Haber s process, Sulphuric acid by Contact process and Potassium dichromate from chromite. Uses of the above compounds. Chemical properties of Sulphuric acid: Action with metals, Dehydrating nature, Oxidation reactions and Reaction with PCI Chemical properties of potassium dichromate: With KOH, Oxidation reactions, formation of chromyl chloride. GROUP 18, NOBEL GASES Applications of noble gases. Isolation of rare gases from Ramsay and Raleigh s Method and separation of individual gases from noble gas mixture (Dewar s charcoal adsorption method).preparation of Pt XeF6 by Neil Bartlett. d - BLOCK ELEMENTS (TRANSITION ELEMENTS) Definition. 3d series: electronic configurations, size, variable oxidation states, colour, magnetic properties, catalytic behaviour, complex formation and their interpretations. THEORY OF DILUTE SOLUTIONS Vant Hoffs theory of dilute solutions, colligative property. Examples of colligative propertieslowering of vapour pressure, elevation in boiling points, depression in freezing point and osmotic pressure. Lowering of vapour pressure-raoult s law (mathematical form to be assumed). Ideal and non-ideal solutions (elementary idea) - measurement of relative lowering of vapour pressure-ostwald and Walker s dynamic method. Determination of molecular mass by lowering of vapour pressure). Numerical problems. COLLOIDS Introduction. Colloidal system and particle size. Types of colloidal systems. Lyophilic and lyiphobic sols, examples and differences. Preparation of sols by Bredig s arc method and peptisation. Purification of sols-dialysis and electro dialysis. Properties of sols-tyndall effect, Brownian movement electrophoresis, origin of charge, coagulation, Hardy and Schulze rule, Protective action of sols. Gold number. Gold number of gelatin and starch. Applications of colloids. Electrical precipitation of smoke, clarification of drinking water and formation of delta 11 P age